Compounds of the n-dihydro-1,2,2&#39;,1&#39;-anthraquinone azine series and process for the production thereof



Patented Feb. 18, 1936 UNHTED STATES PATENT QFFICE 2,030,876 COMPOUNDS -OF THE N-DIHYDRO-1,2,2',1'-

ANTHRAQUINONE AZINE SERIES AND PROCESS FOR THE PRODUCTION THERE- OF Frank Willard Johnson,

Pennsgrove, N. J., as-

signor to E. I. du Pont de Nemours & Company,

Wilmington,

Del., a corporation of Delaware No Drawing. Application July 27, 1932, Serial No. 625,213

13 Claims.

This invenion relates to carbon compounds, more particularly anthraquinone derivatives, and processes for the production thereof.

It is known that certain anthraquinone derivatives may be condensed to produce compounds of higher molecular weight, many of which are valuable dyes. Thus, various methods have been proposedfor the production of N-dihydro-1,2,2',1'- anthraquinone azine, for example, by the conr e densation of 2-ammo-anthraqumone in a caustic m-atlon of dye takes place The melt 1S dflut j 10? with solvent naphthaand filtered. After wash alkali fusion. This procedure is attended by cert 1 d t t th mg out the naphthalene with solvent naphtha commercial var} ages tnheren m e the latter is removed withalcohol and the product use of concentrated caustic alkah. i

finally washed with water. The dye is obtained It IS an obaect of the present invention to prol i 1n beautiful b-ronzy blue crystals in an excellent vlde a new and improved process for producing state of purity anthraquinone condensation products. A fur- Example H ther object is to produce N-dihydro-l,2,2',1'-anthraquinone azine and derivatives thereof by a Ten (10) parts of 2-anuno-1,3-d1ch1oranthradirect method using raw materials which have quinone, 7.0 parts of anhydrous sodium acetate, 0.5 never been successfully employed for this purpart of cuprous iodide and 100 parts of naphtha- 2o; pose. A still further object is the production of leneare heated together at about 185 C. with good chlorine derivatives of N -dihydro-1,2,2,1'-anagitation until no more dye is formed and the rethraquinone azine. Another object is the producsultant solid product is recovered as described in tion of chlorine derivatives of N-dihydro-1,2,2,1'- Example I. It is a blue dye yielding dyeings of exanthraquinone azine by a method which is easily cellent fastness to light, soap, boiling and chlorine 25 controlled to produce products containing any and having most probably the following struc-. desired amount of chlorine within the range of tural formula: about 0-13.9%. Other objects will appear here- 0 inafter.

These objects are accomplished according to O1 307 this invention by condensing 2-amino-1-chloroanthraquinone or a derivative thereof, in the NH Q presence of cuprous iodide, preferably by heating 5 the 2-amino-1-chloronthraquinone (or derivative) in a suitable liquid reaction medium together with the cuprous iodide and an acid-binding agent, e. g. sodium acetate. In practicing the A invention, the reaction mixture should preferably be stirred or agitated. The product may be Example III 40 ga m any Suitable manner for examp by Five (5) parts of 2-amino-l-chloranthraenng and washing out the solvent or susqumone, 5 parts of 2-armno-1,3-d1chloranthrapension medium, acid binder and catalyst with 1 t qmone, 8 parts of dry sodium acetate, 0.75 part so Ven S or by Steam dls 111mg off the Solvent of cuprous iodide and parts of naphthalene after .Which the produPt y be separated by are agitated together at C. until no more 45 filtration washd i wa dye is formed. The naphthalene is then removed Whlle mventlon susciptlkfle conslder by steam distillation and the dye is filtered from able variation and modification 1n the manner the suspension Washed and dried It is a blue of its practical application, particularly as redye containing about 75 by eight of chlorine gards the character of the and yielding dyeings and printings of excellent 50 thraquinone derivatives employed, the catalyst, l ti acid-binding agents, solvent or suspension me- The preparation of the 2-amin0-1-chl0randium, temperatures, proportions of materials, and thraquinone derivatives employed as intermediexact manner of procedure, the following exates in accordance with the present invention is amples will illustrate how the invention may be described in the literature and patents. Thus, 55

practiced. The proportions are given in parts by weight.

Example I 2-amino-l-chloranthraquinone may be obtained by chlorinating 2-amino-anthraquinone, at low temperatures, according to the method described in British Patent 173,166. To obtain the dichloranthraquinoneithe Z-amino-l-chloranthraquinone may be further chlorinated or the methdds described by Junghaus (Ann. 399, 316) (1913) may be used or 2-amino-anthraquinone may be chlorinated by means of sulfuryl chloride in none none suspension. The crude intermediates may be used as such in the condensation, but a better yield and purer product is obtained if they are purified by crystallization from an organic solvent or by dilution of a sulfuric acid solution of the intermediate to a suitable concentration, say 80%, filtering, washing with dilute sulfuric acid and finally boiling up with water. the chlorination of the Z-amino-anthraquinone and the subsequent condensation may be carried out in one medium, without isolation of the intermediate.

The invention is generally applicable to the condensation of 2-amino-l-chloro-anthraquinones. As examples of such compounds may be mentioned:

2-amino-i-chloro-anthraquinone, 2-amino-1- chloro-3-anthraquinone carboxylic acid, 2-amino-1,6-dichloro-anthraquinone, 2-amino-1,7dichloro-anthraquinone, 2-amino-1,3,6-trichloroanthraquinone, Z-amino-l-chloro-B-methyl-anthraquinone, Z-amino-1-chloro-3-ethyl-anthraquinone, 2-amino-1,3-dichloro-6-methyl-anthraquinone, 2-amino-1,3-dichloro-6-nitro-anthraquinone, Z-amino-1-chloro-3-brom-anthraquinone, 2-amino-1-chloro-3-benzoyl-anthraquinone, 2 amino 1 chloro 3-benzoylamino-anthraquinone, 2-amino-1-chloro-3-ethoxy-anthraquinone, 2-amino-1-chloro-3-anthraquinone sulfonic acid, 2- amino 1 -chloro 4 -methyl-anthraquinone, 2- amino l-chloro-4-ethyl-anthraquinone, z-amino- 1 chloro 4 phenyl anthraquinone, chloro-1-benzyl-anthraquinone, Z-amino-l-chloro-S-methoxy-anthraquinone, and the like.

The process is especially advantageous in its application to the condensation of mixtures of Z-amino-l-chloro-anthraquinone and 2-amino- 1,3-dichloro-anthraquinone obtained by any suitable method, for instance by mixing the components together or by chlorinating Z-aminoanthraquinone so that it contains more than about 13.8% by weight of chlorine but less than about 24.2% chlorine. The resultant product may contain any desired amount of chlorine less than about 13.9%. These products are characterized by excellent fastness to light, soap and boiling water and are particularly valuable for textile printing.

The temperature employed in the condensation may vary within relatively wide limits depending largelyupon the nature of the intermediate but shouldvpreferably be above about 150? C. and below the temperature giving rise to decomposition of the reactants and products. Generally speaking, it is desirable to employ temperatures within the range of about 165-190 C. and especially desirableresults have been obtained when the temperature employed was about 1'75-185 C.

The nature and proportions of the acid-binding agent and solvent or suspending medium employed in the condensation are also subject to considerable variation. As acid-binding agents sodium acetate and/or sodium carbonate are preferably employed, the proportions thereof being preferably in excess of the amount required to neutralize the acid set free by the condensa- If desired,

2-amino-1- tion reaction. As examples of high boiling solvents or suspending media naphthalene, nitrobenzene, chlorobenzenes and nitro-toluenes may be mentioned.

It will be understood that other acid-binding agents such as sodium bicarbonate, alkaline earth hydroxides, etc., may be used and other solvents or suspension media which are liquids at the reaction temperature and which are inert or do not affect the reaction unfavorably are suitable reaction media. It will be further recognized that certain additions may be made to the melt for specific purposes, such as compounds having a reducing action (e. g. hydrogenated naphthalene, sodium phenolate, etc.) to reduce the amount of oxidation.

' Instead of introducing cuprous iodide into the reaction mixture as such, mixtures of salts such as may be expected under the conditions of the condensation to react, at least in part, to give cuprous iodide may be employed. Such mixtures are for example, copper acetate and/or copper carbonate with sodium iodide, potassium iodide,

calcium iodide and/or barium iodide.

The advantages of the invention will be apparent. Insofar as is known, it has not heretofore been possible to produce anthraquinone derivatives of the character herein described by the condensation of 2-amino-1-chloro-anthraquinones. Furthermore, the processes previously known are not amenable to the direct formation of chlorine derivatives of N-dihydro-1,2,2,1'- anthraquinone azine containing less than 13.9% by weight of chlorine. These products, particularly those containing about 7-8% chlorine, are very valuable for both printing and dyeing.

- As many apparent and widely different embodiments of this invention may be made without departing from the spirit thereof, it is to be understood that I do not limit myself to the foregoing examples or description except as indicated in the following claims.

I claim:

1. In a process of preparing condensation products of the anthraquinone series, the step which comprises condensing a Z-amino-l-chloro-anthraquinone in the presence of cuprous iodide.

2. In a process of preparing condensation products of the anthraquinone series, the step which comprises heating a Z-amino-l-chloro-anthraquinone in the presence of cuprous iodide, an acid binding agent, and an inert liquid reaction medium.

3. The process of preparing condensation products of the anthraquinone series which comprises heating a 2-amino-l-chloro-anthraquinone at a temperature above about 150 C. in the presence of cuprous iodide, an acid binding agent, and an inert liquid reaction medium.

4. The process of producing N-dihydro-1,2,2,1- anthraquinone azine which comprises condensing 2-amino-l-chloro-anthraquinone in the presence of cuprous iodide.

5. The process of producing N-dihydro-1,2,2',l'- anthraquinone azine which comprises heating 2- amino-l-chloro-anthraquinone to a temperature of about 175-185 iodide, substantially dry sodium acetate and an inert liquid reaction medium.

6. The process which comprises agitating 2- amino-l-chloro-anthraquinone in naphthalene at a temperature of about 175-185 C. and in the presence of cuprous iodide and anhydrous sodium acetate.

C. in the presence of cuprous,

7. In a process of preparing condensation prodnets of the anthraquinone series, the step which comprises condensing a 2-amino-1-chloroanthraquinone in the presence of a copper salt and an iodine salt capable of reacting at least in part to form cuprous iodide.

8. A process of preparing chloro-N-dihydro- 1,2,2',1-anthraquinone azines which comprises condensing a chlorinated 2-amino-anthraquinone having a chlorine content within the range of about 13.824.2% by weight, in the presence of cuprous iodide.

9. The process of producing chloro-N-dihydro-1,2,2,1'-anthraquinone azine suitable for both dyeing ing a mixture of about equal parts of 2-amino-1- chloro-anthraquinone and 2-amino-1,3-dichloroanthraquinone to a temperature of about 175- 185 C. in an inert organic solvent medium, in the presence of cuprous iodide and at least suificient substantially dry sodium acetate to neutralize the liberated hydrogen chloride.

10. A process of preparing halogen-N-hydroand printing, which comprises heat- 1,2,2',1'-anthraquinone azines which comprises heating 2-amino-1-chloro-3-halogen-anthraquinone in the presence of cuprous iodide, an acid binding agent and an inert liquid reaction medium.

11. A process of preparing chloro-N-dihydro- 1,2,2',1'-anthraquinone azines which comprises heating 2-amino-1,3-dichloro-anthraquinone in the presence of cuprous iodide, an acid binding agent and an inert liquid reaction medium.

12. In a process of preparing condensation products of the anthraquinone series, the step which comprises heating a Z-amino-l-chloro-anthraquinone in the presence of an acid binding agent, an inert liquid reaction medium, and a copper salt and an iodine salt capable of reacting at least in part to form cuprous iodide.

13. In a process of producing N-dihydro- 1,2,2',1'-anthraquinone azine, the step which comprises condensing together two molecules of 2- amino-1-chloro-anthraquinone.

FRANK WILLARD JOHNSON. 

